EP4227089A1 - Film multicouche et matériau d'emballage - Google Patents

Film multicouche et matériau d'emballage Download PDF

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Publication number
EP4227089A1
EP4227089A1 EP21877532.8A EP21877532A EP4227089A1 EP 4227089 A1 EP4227089 A1 EP 4227089A1 EP 21877532 A EP21877532 A EP 21877532A EP 4227089 A1 EP4227089 A1 EP 4227089A1
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EP
European Patent Office
Prior art keywords
resin
resin layer
hydroxyalkanoate
layer
multilayer film
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
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EP21877532.8A
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German (de)
English (en)
Inventor
Wei Miao
Takeshi Sugiyama
Arihiro Saito
Shun MURASAWA
Tetsuo Okura
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Kaneka Corp
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Kaneka Corp
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Publication date
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Publication of EP4227089A1 publication Critical patent/EP4227089A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/02—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage
    • B65D81/05—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage maintaining contents at spaced relation from package walls, or from other contents
    • B65D81/051—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents specially adapted to protect contents from mechanical damage maintaining contents at spaced relation from package walls, or from other contents using pillow-like elements filled with cushioning material, e.g. elastic foam, fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/244—All polymers belonging to those covered by group B32B27/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/58—Cuttability
    • B32B2307/581—Resistant to cut
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a multilayer film including a resin layer containing a poly(3-hydroxyalkanoate) resin and a packaging material in which the multilayer film is used.
  • Poly(3-hydroxyalkanoate) resins are highly degradable in seawater and can be a solution to the environmental problems induced by discarded plastics.
  • poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is one of the poly(3-hydroxyalkanoate) resins, and the mechanical properties of this resin can be flexibly controlled by changing the proportion of 3-hydroxyhexanoate.
  • the poly(3-hydroxyalkanoate) resins have higher gas barrier performance and are more resistant to hydrolysis than other biodegradable resins and are promising for a wide range of applications such as the use in packaging materials.
  • a multilayer film containing a poly(3-hydroxyalkanoate) resin is described, for example, in Patent Literature 1.
  • the multilayer film of Patent Literature 1 includes a layer containing a poly(3-hydroxyalkanoate) resin and another biodegradable resin and a layer having a poly(3-hydroxyalkanoate) resin content of less than 10 wt%.
  • Patent Literature 2 describes a multilayer film including a layer made of a composition containing a poly(3-hydroxyalkanoate) resin and destructurized starch and a layer made of a poly(3-hydroxyalkanoate) resin.
  • multilayer films may be used as films for heat sealing in which the films are thermally fused into the form of a pouch in order to increase the airtightness and shelf life of the food products.
  • Patent Literatures 1 and 2 fail to specifically discuss the use of multilayer films in heat sealing.
  • the present invention aims to provide a multilayer film that includes a resin layer containing a poly(3-hydroxyalkanoate) resin, that has high heat sealability, and whose base layer is resistant to deformation during heat sealing.
  • a multilayer film including two layers each of which contains a poly(3-hydroxyalkanoate) resin can be a solution to the problem when the thickness ratio between the two layers is set in a given range and heat quantities ⁇ H of the layers are set in given ranges, respectively. Based on this finding, the inventors have completed the present invention.
  • the thickness of the first resin layer is from 10 to 300 ⁇ m.
  • the poly(3-hydroxyalkanoate) resin includes a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units.
  • the poly(3-hydroxyalkanoate) resin of the first resin layer is a copolymer which is a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units and in which a content of the other hydroxyalkanoate units is from 1 to 7 mol%
  • the poly(3-hydroxyalkanoate) resin of the second resin layer is a copolymer which is a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units and in which a content of the other hydroxyalkanoate units is from 7 to 20 mol%
  • the content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin of the second resin layer is higher than the content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin of the first resin layer.
  • the other hydroxyalkanoate units are 3-hydroxyhexanoate units.
  • the first and second resin layers are integral with each other.
  • the thickness of the first resin layer is from 10 to 300 ⁇ m, and the thickness of the second resin layer is from 5 to 70 ⁇ m.
  • the first resin layer and/or the second resin layer further contains a nucleating agent.
  • the nucleating agent includes at least one selected from the group consisting of poly(3-hydroxybutyrate) (P3HB), talc, a fatty acid amide, a nucleic acid base, and a dipeptide.
  • the multilayer film is adapted for heat sealing.
  • the present invention further relates to a method for producing the multilayer film, the method including the steps of (A) forming each of the first and second resin layers individually by blown film molding or T-die molding; and (B) integrating the first and second resin layers obtained in the step (A) by thermal lamination, or the method including the step of forming the first and second resin layers together by multilayer blown film molding or multilayer T-die molding.
  • the present invention further relates to a packaging material including the multilayer film.
  • the packaging material is in the form of a pillow pack.
  • the present invention can provide a multilayer film that includes a resin layer containing a poly(3-hydroxyalkanoate) resin, that has high heat sealability, and whose base layer is resistant to deformation during heat sealing.
  • FIG. 1 illustrates a heat quantity ⁇ H in an example of a DSC curve measured for a resin layer.
  • a multilayer film according to one embodiment of the present invention includes first and second resin layers each of which contains a poly(3-hydroxyalkanoate) resin.
  • the multilayer film can be used as a multilayer film for heat sealing.
  • the first resin layer can serve as a base layer
  • the second resin layer can serve as a heat sealing layer.
  • the second resin layer serving as a heat sealing layer may be disposed over only one side of the first resin layer serving as a base layer or over both sides of the first resin layer.
  • the second resin layer may be disposed over the first resin layer with another layer interposed between the first and second resin layers or may be disposed directly on the first resin layer without any other layer interposed between the first and second resin layers.
  • Each of the first and second resin layers contains at least a poly(3-hydroxyalkanoate) resin.
  • the poly(3-hydroxyalkanoate) resin is preferably a polymer containing 3-hydroxyalkanoate units, in particular a polymer containing units represented by the following formula (1). [-CHR-CH 2 -CO-O-] (1)
  • R is an alkyl group represented by C p H 2p+1 , and p is an integer from 1 to 15.
  • R group include linear or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl groups.
  • the integer p is preferably from 1 to 10 and more preferably from 1 to 8.
  • the poly(3-hydroxyalkanoate) resin is particularly preferably a microbially produced poly(3-hydroxyalkanoate) resin.
  • microbially produced poly(3-hydroxyalkanoate) resin all of the 3-hydroxyalkanoate units are contained as (R)-3-hydroxyalkanoate units.
  • the poly(3-hydroxyalkanoate) resin contains 50 mol% or more of 3-hydroxyalkanoate units (in particular, the units represented by the formula (1)) in the total structural units, and the content of the 3-hydroxyalkanoate units is more preferably 60 mol% or more and even more preferably 70 mol% or more.
  • the poly(3-hydroxyalkanoate) resin may contain only one type or two or more types of 3-hydroxyalkanoate units as polymer structural units or may contain other units (such as 4-hydroxyalkanoate units) in addition to the one type or two or more types of 3-hydroxyalkanoate units.
  • the poly(3-hydroxyalkanoate) resin is preferably a homopolymer or copolymer containing 3-hydroxybutyrate (hereinafter also referred to as "3HB") units.
  • 3-hydroxybutyrate units are preferably (R)-3-hydroxybutyrate units.
  • the poly(3-hydroxyalkanoate) resin is preferably a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units.
  • the copolymerization is not limited to a particular type and may be random copolymerization, alternating copolymerization, block copolymerization, or graft copolymerization.
  • poly(3-hydroxyalkanoate) resin examples include poly(3-hydroxybutyrate) abbreviated as "P3HB", poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) abbreviated as "P3HB3HV”, poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) abbreviated as "P3HB3HH", poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) abbreviated
  • P3HB3HH, P3HB3HV, and P3HB4HB are preferred, and P3HB3HH and P3HB4HB are more preferred.
  • P3HB which is a homopolymer, can be used also as a nucleating agent as described later.
  • P3HB3HH is particularly preferred for the following reasons: the ratio between the repeating units can be varied to change the melting point and crystallinity and thus adjust the physical properties such as the Young's modulus and heat resistance to levels intermediate between those of polypropylene and polyethylene; and this plastic is easy to industrially produce as mentioned above and useful in terms of physical properties.
  • P3HB3HH is preferred also in that it can have a low melting point and be moldable at low temperature.
  • each of the first and second resin layers preferably contains a copolymer of 3-hydroxybutyrate units and other hydroxyalkanoates and particularly preferably contains P3HB3HH (poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)).
  • the layer may contain only one such copolymer or at least two such copolymers differing in the types and/or contents of the constituent monomers.
  • Each of the layers may contain at least one such copolymer and P3HB.
  • the copolymer of the first resin layer and the copolymer of the second resin layer differ in the types and/or contents of the constituent monomers such that requirements concerning heat quantities ⁇ H as described later are satisfied.
  • the content of the other hydroxyalkanoate units (in particular, 3-hydroxyhexanoate units) in the copolymer of the second resin layer is preferably higher than the content of the other hydroxyalkanoate units (in particular, 3-hydroxyhexanoate units) in the copolymer of the first resin layer.
  • the second resin layer has a smaller value of heat quantity ⁇ H and a lower melting point than the first resin layer; thus, upon heating in heat sealing, the second resin layer tends to readily melt even as the first resin layer resists melting. This can prevent deformation of the base layer and at the same time allow the heat sealing layer to exhibit high heat sealability.
  • the content of the other hydroxyalkanoate units is preferably from 1 to 7 mol%, more preferably from 3 to 7 mol%, and even more preferably from 5 to 7 mol%.
  • the content of the other hydroxyalkanoate units is preferably from 7 to 20 mol%, more preferably from 8 to 20 mol%, even more preferably from 8 to 15 mol%, and still even more preferably from 9 to 13 mol%.
  • the content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin of the second resin layer is higher than the content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin of the first resin layer.
  • the average content of certain monomer units in the total monomer units constituting a poly(3-hydroxyalkanoate) resin can be determined by a method known to those skilled in the art, such as by a method described in paragraph [0047] of WO 2013/147139 .
  • the "average content" of certain monomer units refers to the average content of the monomer units contained in the total mixture.
  • the weight-average molecular weight of the poly(3-hydroxyalkanoate) resin of the first resin layer is preferably from 20 ⁇ 10 4 to 250 ⁇ 10 4 , more preferably from 25 ⁇ 10 4 to 230 ⁇ 10 4 , even more preferably from 30 ⁇ 10 4 to 200 ⁇ 10 4 , and particularly preferably from 35 ⁇ 10 4 to 150 ⁇ 10 4 .
  • the weight-average molecular weight of the poly(3-hydroxyalkanoate) resin of the first resin layer is in the above range, deformation of the first resin layer due to heating during heat sealing can be more effectively prevented.
  • the weight-average molecular weight of the poly(3-hydroxyalkanoate) resin of the second resin layer is preferably from 5 ⁇ 10 4 to 100 ⁇ 10 4 , more preferably from 10 ⁇ 10 4 to 80 ⁇ 10 4 , even more preferably from 15 ⁇ 10 4 to 60 ⁇ 10 4 , and particularly preferably from 15 ⁇ 10 4 to 50 ⁇ 10 4 .
  • the weight-average molecular weight of the poly(3-hydroxyalkanoate) resin of the second resin layer is in the above range, the second resin layer subjected to heat sealing can exhibit a higher bond strength.
  • the method for measuring the weight-average molecular weight of each poly(3-hydroxyalkanoate) resin is not limited to a particular technique.
  • the weight-average molecular weight can be determined as a polystyrene-equivalent weight-average molecular weight by using chloroform as a mobile phase, GPC system manufactured by Waters Corporation as a chromatography system, and Shodex K-804 (polystyrene gel) manufactured by Showa Denko K.K. as a column.
  • the method for producing each poly(3-hydroxyalkanoate) resin is not limited to a particular technique, and may be a chemical synthesis production method or a microbial production method.
  • a microbial production method is more preferred.
  • the microbial production method used can be any known method.
  • Known examples of bacteria that produce copolymers of 3-hydroxybutyrate with other hydroxyalkanoates include Aeromonas caviae which is a P3HB3HV- and P3HB3HH-producing bacterium and Alcaligenes eutrophus which is a P3HB4HB-producing bacterium.
  • Aeromonas caviae which is a P3HB3HV- and P3HB3HH-producing bacterium
  • Alcaligenes eutrophus which is a P3HB4HB-producing bacterium.
  • Alcaligenes eutrophus AC32 (FERM BP-6038; see T.
  • a microorganism having a poly(3-hydroxyalkanoate) resin synthase gene introduced is more preferred.
  • Such a microorganism is cultured under suitable conditions to allow the microorganism to accumulate P3HB3HH in its cells, and the microbial cells accumulating P3HB3HH are used.
  • a genetically modified microorganism having any suitable poly(3-hydroxyalkanoate) resin synthesis-related gene introduced may be used depending on the poly(3-hydroxyalkanoate) resin to be produced.
  • the culture conditions including the type of the substrate may be optimized depending on the poly(3-hydroxyalkanoate) resin to be produced.
  • Microbially produced P3HB3HH is a random copolymer.
  • the adjustment of the 3HH unit content of microbially produced P3HB3HH can be accomplished, for example, by selection of a suitable bacterium, by selection of a suitable carbon source as a raw material, by blending of two or more types of P3HB3HH having different 3HH unit contents, or by addition of a homopolymer of 3HB.
  • P3HB3HH is "Kaneka Biodegradable Polymer PHBH TM" of Kaneka Corporation.
  • the first or second resin layer may contain one or two or more additional resins in addition to the poly(3-hydroxyalkanoate) resin so long as the effect of the invention is achieved.
  • the additional resins are preferably biodegradable resins, examples of which include: aliphatic polyester resins such as polybutylene succinate, polybutylene succinate adipate, polycaprolactone, and polylactic acid; and aliphatic-aromatic polyester resins such as polybutylene adipate terephthalate, polybutylene sebacate terephthalate, and polybutylene azelate terephthalate.
  • the amount of the additional resins is preferably small in order to ensure the seawater degradability of the multilayer film.
  • the amount of the additional resins contained in the multilayer film is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight per 100 parts by weight of the multilayer film.
  • the lower limit of the amount of the additional resins is not limited to a particular value and may be 0 part by weight.
  • the first or second resin layer may further contain a nucleating agent so long as the effect of the invention is achieved.
  • the nucleating agent provides an improving effect on moldability, productivity, etc.
  • the nucleating agent is not limited to a particular type and may be any nucleating agent that provides the above effect.
  • the nucleating agent include poly(3-hydroxybutyrate) (P3HB), talc, fatty acid amides, nucleic acid bases (such as adenine, guanine, thymine, cytosine, uracil, and their derivatives), dipeptides (such as glycylglycine and glycyl-L-leucine), pentaerythritol, orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, and boron nitride.
  • P3HB poly(3-hydroxybutyrate)
  • talc talc
  • fatty acid amides such as adenine, guanine, thymine, cytosine, uracil, and their derivatives
  • dipeptides such as glycylgly
  • pentaerythritol is preferred because it is particularly superior in accelerating effect on crystallization of the poly(3-hydroxyalkanoate) resin.
  • One of these nucleating agents may be used alone, or two or more thereof may be used in combination.
  • the amount of the nucleating agent contained in the first or second resin layer is preferably 10 wt% or less and more preferably 7 wt% or less so that the viscosity during the film production process and the physical properties of the multilayer film may fall within suitable ranges.
  • the lower limit of the amount of the nucleating agent is not limited to a particular value and may be 0 wt%.
  • the amount of the nucleating agent is preferably 1 wt% or more and more preferably 3 wt% or more.
  • the amount of the nucleating agent contained in the first or second resin layer is preferably 5 wt% or less and more preferably 3 wt% or less so that the viscosity during the film production process and the physical properties of the multilayer film may fall within suitable ranges.
  • the lower limit of the amount of the nucleating agent is not limited to a particular value and may be 0 wt%.
  • the amount of the nucleating agent is preferably 0.1 wt% or more and more preferably 0.5 wt% or more.
  • the second resin layer is preferably free of any nucleating agent other than P3HB in terms of ensuring high heat sealability.
  • the first or second resin layer may contain additives commonly used in the technical field so long as the effect of the invention is achieved.
  • the additives include: inorganic fillers such as talc, calcium carbonate, mica, silica, titanium oxide, and alumina; organic fillers such as chaff, wood powder, waste paper (e.g., newspaper), various kinds of starch, and cellulose; colorants such as pigments and dyes; odor absorbers such as activated carbon and zeolite; flavors such as vanillin and dextrin; and various other additives such as plasticizers, oxidation inhibitors, antioxidants, weathering resistance improvers, ultraviolet absorbers, lubricants, mold releases, water repellents, antimicrobials, slidability improvers, tackifiers, fillers, crosslinking agents (e.g., peroxides), and chemicals.
  • the first or second resin layer may contain only one additive or may contain two or more additives. The amount of the additives can be set by those skilled in the art as
  • the layer thickness ratio described later is within a given range, a heat quantity ⁇ H of the first resin layer is equal to or greater than a given value, and a heat quantity ⁇ H of the second resin layer is equal to or smaller than a given value.
  • the multilayer film can exhibit high heat sealing strength and at the same time resist deformation of the base layer during heat sealing.
  • the heat quantity ⁇ H of the first resin layer is set to 30 J/g or more, and the heat quantity ⁇ H of the second resin layer is set to 25 J/g or less.
  • the second resin layer Since the heat quantity ⁇ H of the first resin layer and the heat quantity ⁇ H of the second resin layer are set to given different ranges as described above, the second resin layer has a lower melting point than the first resin layer. Thus, upon heating in heat sealing, the second resin layer tends to readily melt even as the first resin layer resists melting. This can prevent deformation of the base layer and at the same time allow the heat sealing layer to exhibit high heat sealability.
  • the heat quantity ⁇ H of the first resin layer is preferably 32 J/g or more, more preferably 35 J/g or more, and even more preferably 38 J/g or more.
  • the upper limit of the heat quantity ⁇ H is not limited to a particular value.
  • the heat quantity ⁇ H is typically 100 J/g or less, preferably 70 J/g or less, and more preferably 50 J/g or less.
  • the heat quantity ⁇ H of the second resin layer is preferably 24 J/g or less, more preferably 22 J/g or less, even more preferably 20 J/g or less, and particularly preferably 18 J/g or less.
  • the lower limit of the heat quantity ⁇ H is not limited to a particular value.
  • the heat quantity ⁇ H may be 0 J/g or more, and is preferably 5 J/g or more and more preferably 10 J/g or more.
  • the heat quantity ⁇ H of each layer can be controlled in the desired range, for example, by appropriately selecting the types and/or contents of the constituent monomers of the poly(3-hydroxyalkanoate) resin forming the layer.
  • the multilayer film can exhibit high heat sealing strength and at the same time resist deformation of the base layer during heat sealing.
  • the ratio of the thickness of the first resin layer to the thickness of the second resin layer is from 1.0:0.015 to 1.0:5.0.
  • the thickness ratio is preferably from 1.0:0.1 to 1.0:3.3, more preferably from 1.0:0.2 to 1.0:2.5, even more preferably from 1.0:0.3 to 1.0:2.0, and particularly preferably from 1.0:0.5 to 1.0:1.5.
  • the thickness of the first resin layer is not limited to a particular range. In terms of heat sealing strength and resistance to base layer deformation during heat sealing, the thickness of the first layer is preferably from 10 to 300 ⁇ m, more preferably from 20 to 200 ⁇ m, and even more preferably from 30 to 150 ⁇ m. Further, in terms of resistance to base layer deformation during high-temperature heat sealing, the thickness of the first resin layer is preferably 50 ⁇ m or more and more preferably 80 ⁇ m or more. In terms of mechanical strength, the thickness of the first resin layer may be 10 ⁇ m or more or may be 30 ⁇ m or more. In terms of productivity, the thickness of the first resin layer may be 300 ⁇ m or less, may be 100 ⁇ m or less, or may be 70 ⁇ m or less.
  • the thickness of the second resin layer is not limited to a particular range. In terms of heat sealing strength and resistance to base layer deformation during heat sealing, the thickness of the second resin layer is preferably from 5 to 200 ⁇ m, more preferably from 10 to 150 ⁇ m, and even more preferably from 20 to 100 ⁇ m. In terms of productivity, the thickness of the second resin layer may be 70 ⁇ m or less or may be 50 ⁇ m or less.
  • the overall thickness of the multilayer film can be set as appropriate depending on the intended use and other factors.
  • the overall thickness of the multilayer film is preferably 15 ⁇ m or more, more preferably 30 ⁇ m or more, and even more preferably 50 ⁇ m or more in terms of mechanical strength and barrier performance.
  • the overall thickness of the multilayer film is preferably 300 ⁇ m or less, more preferably 250 ⁇ m or less, and even more preferably 200 ⁇ m or less.
  • the overall thickness of the multilayer film may be 150 ⁇ m or less or may be 100 ⁇ m or less.
  • the multilayer film may, if necessary, include an additional layer in addition to the first and second resin layers, and the additional layer may be disposed at any location, such as between the first and second resin layers, outside the first resin layer (on that surface of the first resin layer which faces away from the second resin layer), or outside the second resin layer (on that surface of the second resin layer which faces away from the first resin layer).
  • the additional layer include a barrier layer, a vapor-deposited layer, a print layer, a base layer, a reinforcing layer made of biodegradable resin, and an adhesive layer. There may be only one such additional layer or may be a plurality of such additional layers.
  • the multilayer film preferably includes no additional layer disposed outside the second resin layer serving as a heat sealing layer. That is, the second resin layer is preferably an outermost layer of the multilayer film.
  • the first and second resin layers are preferably integral with each other.
  • the multilayer film can have high piercing resistance.
  • the term "integral" is intended to mean that the first and second resin layers are adjacent and joined directly or indirectly with an additional layer interposed between the first and second resin layers and that part of the resin forming at least one of the first and second resin layers is heat-fused to the other adjacent layer to bond the layers to each other.
  • the term "heat-fused” is intended to mean that a resin melted or softened by heating adheres to another substance.
  • the first and second resin layers are preferably integral with each other such that the peel strength between the layers is 3 N/15 mm or more, more preferably such that the peel strength is 5 N/15 mm or more, and even more preferably such that the peel strength is 6 N/15 mm or more.
  • the peel strength between the first and second resin layers is 3 N/15 mm or more, higher piercing resistance can be achieved.
  • the peel strength between the first and second resin layers is a parameter measured by a method described in Examples below. In the case where the test specimen includes an additional layer between the first and second resin layers, the peel strength between the first and second resin layers refers to a peel strength at the interface where the peeling occurs.
  • the first and second resin layers are adjacent and joined directly, and part of the resin forming one of the layers and part of the resin forming the other layer mix together at the interface between the layers, which are thus bonded to each other.
  • the partial mixing of the resins of the layers at the interface leads to higher piercing resistance.
  • the multilayer film can be produced by multilayer blown film molding, multilayer T-die molding, or extrusion lamination.
  • the multilayer blown film molding and multilayer T-die molding are performed using a multilayer blown film molding device and a multilayer T-die molding device, respectively. In either molding process, molten resin compositions for forming the layers are stacked on each other and co-extruded.
  • At least one of the resin layers is formed as a film, onto which a molten composition for forming the other resin layer is extruded.
  • a molten composition for forming the other resin layer is extruded onto the film.
  • the temperature during extrusion molding can be set as appropriate depending on the properties such as melting point and MFR of the resin compositions for forming the layers.
  • the temperature during extrusion molding is preferably, for example, from 150 to 180°C and more preferably from 155 to 170°C.
  • a suitable method for producing the multilayer film is to form each of the first and second resin layers individually by blown film molding or T-die molding and then integrate the two layers by thermal lamination.
  • the first and second resin layers may be integrated by thermal lamination with the additional layer interposed between the first and second resin layers.
  • the lamination temperature can be set as appropriate depending on the properties such as melting point and MFR of the resin compositions for forming the layers.
  • the lamination temperature is preferably, for example, from 90 to 130°C and more preferably from 95 to 120°C.
  • Yet another method for producing the multilayer film is to form at least one of the resin layers as a film, apply an aqueous coating liquid for forming the other layer to one side or both sides of the film, and heat and dry the applied coating liquid into the other resin layer.
  • the second resin layer whose heat quantity ⁇ H is smaller than that of the first resin layer, has a lower melting point than the first resin layer and can thus exhibit high heat sealability.
  • the multilayer film can be suitably used as a packaging material in an application involving heat sealing.
  • the first resin layer be an outer layer of the packaging material and the second resin layer be an inner layer of the packaging material.
  • the packaging material including the multilayer film By subjecting the packaging material including the multilayer film to heat sealing such that the second resin layer serves as an innermost layer, a packaging pouch or container having sufficient sealing strength can be produced.
  • a particularly preferred embodiment can provide a pillow pack having the second resin layer as a heat sealing layer.
  • heat sealing of the multilayer film for example, two pieces or portions of the multilayer film may be placed on each other such that the second resin layers of the two pieces or portions are in face-to-face contact, and then heat and pressure may be applied to the second resin layers through the first resin layers to melt the second layers and bond the second layers to each other.
  • the heat sealing conditions such as heating temperature, heating time, and pressure are not limited to particular ranges and may be set as per common practice.
  • the heating temperature during heat sealing is preferably from 100 to 150°C and more preferably from 110 to 140°C.
  • Each of the first and second layers was prepared as a single-layer film, which was used as a sample.
  • the measurement was conducted using a DSC system (DSC 214 Polyma manufactured by NETZSCH) over a temperature range of -20 to 190°C at a temperature increase rate of 10°C/min.
  • a DSC curve as shown in FIG. 1 was obtained for each layer.
  • baselines observed before the onset of melting and after the end of melting were connected by a straight line.
  • the area of the region (heat of melting) over the range of 130 to 190°C was determined as the heat quantity ⁇ H of the layer.
  • the heat quantity ⁇ H is a value corresponding to the area of the hatched region in FIG. 1 .
  • the multilayer film was cut into two rectangular pieces with a size of 15 mm ⁇ 8 cm, and the two pieces were stacked on each other and heat-sealed using a heat sealing tester (TP-701-B manufactured by Tester Sangyo Co., Ltd.).
  • the gauge pressure was 0.2 MPa
  • the sealing time was 1 second
  • only the upper one of the sealing bars was heated.
  • the heat sealing was conducted at different temperatures of 110°C, 120°C, 130°C, and 140°C. In the heat sealing, the sealing bars were made in contact with the first layers, and the second layers were placed in face-to-face contact with each other.
  • the heat-sealed sample was subjected to T-peel test using Autograph (AGS-X manufactured by Shimadzu Corporation) at a test speed of 100 mm/min.
  • the state of the first layer was inspected.
  • a score of "Good” was given.
  • a score of "Poor” was given.
  • P3HB3HH-1 which is shown as the resin of the first layer in Table 1
  • a nucleating agent 0.5 parts by weight of a nucleating agent.
  • the mixture was kneaded using a twin-screw extruder (TEM 26 manufactured by Toshiba Machine Co., Ltd.) at a barrel temperature of 150°C, a screw rotational speed of 100 rpm, and a discharge rate of 10 kg/h.
  • the melted and kneaded mixture was extruded into a strand from a die, and the strand was put into a water bath heated to 40°C to solidify the strand.
  • the solidified strand was cut by a pelletizer, and thus resin composition pellets were obtained.
  • an blown film molding machine manufactured by Hokushin Sangyo Co., Ltd.
  • P3HB3HH-2 which is shown as the resin of the second layer in Table 1, was used to obtain resin composition pellets under the conditions as described above.
  • the pellets were then processed under the conditions as described above, and thus a 35- ⁇ m-thick resin film (second layer) was obtained.
  • the obtained films were aged at 50°C for 1 week, after which the first and second layers were stacked on each other and bonded together using a vacuum laminator (Module Laminator LM-50 ⁇ 50-S manufactured by NPC Incorporated) at a temperature of 100°C and a pressure of 2 atmospheres. As a result, a multilayer film was obtained.
  • a vacuum laminator Module Laminator LM-50 ⁇ 50-S manufactured by NPC Incorporated
  • Multilayer films were obtained and evaluated in the same manner as in Example 1, except that the types of the resins used were changed as shown in Table 1 and that the thicknesses of the resin films were changed as shown in Table 1. The evaluation results obtained are summarized in Table 1. [Table 1] Example 1 Example 2 Example 3 Example 4 Comp. Example 1 Comp.
  • Example 1 reveals the following findings.
  • the heat sealing was accomplished without damage to the base layer over the heat sealing temperature range of 110 to 130°C.
  • Good results were obtained over the heat sealing temperature range of 130 to 140°C in Example 2, at a heat sealing temperature of 130°C in Example 3, and over the heat sealing temperature range of 110 to 130°C in Example 4.
  • Comparative Example 1 the heat sealing was not accomplished without damage to the base layer at any heat sealing temperatures.
  • Comparative Example 2 although the heat sealing was accomplished without damage to the base layer at a heat sealing temperature of 140°C, the sealing strength was not sufficiently high.
  • P3HB3HH-4 Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a copolymerization component ratio, (3-hydroxybutyrate)/(3-hydroxyhexanoate), of 93.8/6.2 (mol/mol) and a weight-average molecular weight of 60 ⁇ 10 4 .
  • P3HB3HH-5 Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a copolymerization component ratio, (3-hydroxybutyrate)/(3-hydroxyhexanoate), of 92.3/7.7 (mol/mol) and a weight-average molecular weight of 60 ⁇ 10 4 .
  • test specimen was fixed in place with a jig and pierced with a half-round needle having a diameter of 1.0 mm and a tip radius of 0.5 mm at a test speed of 50 ⁇ 5 mm/min.
  • the integral of the test force (N) with respect to the stroke from the start of the test to the moment when the needle penetrated through the test specimen was calculated in units of mJ.
  • Two films with a suitable size were stacked on each other and subjected to an integrating process (thermal lamination described later) such that one edge of the resulting two-layer film was able to be used as a peel strength measurement area.
  • the sample thus obtained was cut to give a 15-mm-wide test specimen.
  • the test specimen was opened to 180° and its two ends were attached to grips of a tensile tester such that the peel strength measurement area of the test specimen was located at the middle between the grips.
  • the test specimen was pulled until peeling or breakage occurred, and the maximum force (N) was determined and recorded as the peel strength.
  • the test speed was 300 mm/min.
  • Two films with a suitable size were stacked on each other, and one edge of the stack of the films was heat-sealed at a lamination temperature of 110°C and a pressure of 0.1 MPa.
  • the sample thus obtained was cut to give a 15-mm-wide test specimen.
  • the test specimen was opened to 180° and its two ends were attached to grips of a tensile tester such that the heat-sealed portion of the test specimen was located at the middle between the grips.
  • the test specimen was pulled until the heat-sealed portion broke, and the maximum force (N) was determined.
  • the distance between the grips was 50 mm or more at the start of the test.
  • the test speed was 300 mm/min.
  • the first and second layers obtained as above were bonded together by thermal lamination at a lamination temperature of 110°C and a pressure of 0.1 MPa.
  • a laminated film 60 ⁇ m thick
  • the first layer (30 ⁇ m thick) and the second layer (30 ⁇ m thick) was obtained.
  • the piercing resistance, peel strength, and heat sealability were measured by the methods described above. The results are shown in Table 2.
  • Example 6 First layer Resin P3HB3HH-4 P3HB3HH-4 P3HB3HH-4 Latent heat ⁇ H [J/g] 42 42 42 Layer thickness [um] 30 60 30 Second layer Resin P3HB3HH-5 P3HB3HH-5 P3HB3HH-5 Latent heat ⁇ H [J/g] 25 25 25 Layer thickness [um] 30 60 30 Piercing resistance [mJ] 12.8 7.5 7.9 3.7 3.9 Peel strength [N/15 mm] 8 - - - - Heat sealability [N/15 mm] > 5 - - - - - -
  • the laminated film of Example 5 which included the first and second layers, had higher piercing resistance than the single-layer films of Comparative Examples 3 and 4 each of which consisted only of either the first or second layer, despite the fact that the film of Example 5 had the same thickness as the films of Comparative Examples 3 and 4. Additionally, as seen from Table 2, the piercing resistance of the laminated film of Example 5 was twice or more those of the single-layer films of Comparative Examples 5 and 6 each of which had a thickness of 30 ⁇ m equal to half the thickness of the film of Example 5.

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